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2008

Effect of titanium additions to low carbon, low

manganese steels on sulphide precipitation
Sima Aminorroaya-Yamini
University of Wollongong, sima@uow.edu.au

Recommended Citation
Aminorroaya-Yamini, Sima, Effect of titanium additions to low carbon, low manganese steels on sulphide precipitation, PhD thesis,
Engineering Materials Institute, University of Wollongong, 2008. http://ro.uow.edu.au/theses/403

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Effect of titanium additions to low
carbon, low manganese steels on
sulphide precipitation

A thesis submitted in fulfillment of the

requirements for the award of the degree of

Doctor of Philosophy

From
University of Wollongong

By
SIMA AMINORROAYA-YAMINI
BSc.(Mat), MSc. (Mat)

Engineering Materials Institute

2008
 Certification

I, Sima Aminorroaya, declare that this thesis, submitted in fulfillment of the

requirement for the award of Doctor of Philosophy, in the Engineering Materials
Institute, University of Wollongong, is wholly my own work unless otherwise
referenced or acknowledged. The document has not been submitted for qualifications
at any other academic institution.

Sima Aminorroaya-Yamini
2008

II
 ABSTRACT

Recent developments of high strength line pipe steel have seen a decrease in carbon
content from 0.25 wt% to less than 0.05 wt% and manganese to less than 1 wt% in an
attempt to reduce centreline segregation. The sulphur content should be less than
0.008 wt% as well. However, recent papers argued that low manganese levels in
pipeline steels have the potential to improve weld line toughness and allow a higher
tolerance for sulphur. Should this be true it would be possible to eliminate the usual
desulphurising treatments thereby decreasing the production cost. The current study
was designed to explore the effect of titanium on sulphide precipitation in steels with
higher sulphur contents than currently used in the pipeline industry.

The mechanical properties of steels are influenced by the type, shape and size of
sulphide precipitates. Titanium additions to low carbon steel influence the
precipitation behavior and composition of sulphide precipitates and could provide
grain refinement, precipitation strengthening and sulphide shape control. In the
present study, titanium was added to a low carbon, low manganese steel which
contained approximately 0.01 wt% sulphur in order to study the effect of titanium on
sulphide formation in the absence of other alloying elements.

Microscopic assessment of centreline sulphide precipitates revealed that iron-

titanium-sulphide co-exists with (Mn,Fe)S. An increase of the titanium content from
0.008 wt% to 0.024 wt%, results in an increase in the titanium content of iron-
titanium-sulphide phases and a decrease in the iron content of the (Mn,Fe)S phases.
In contrast to reports in the literature where it has been suggested that titanium can
dissolve in MnS and even that it is possible for TiS to replace MnS. This study has
shown that Ti replaces iron in FeS but does not dissolve in manganese sulphides. The
presence of FeTiS2 (trigonal CdI2-type structure with a P3m1 space group and lattice
parameters of a = 0.34 nm and c = 0.57 nm) precipitates has been verified for the first
time in steel.

III
A concentric solidification technique in a laser-scanning confocal microscope was
employed to observe in situ, solidification and the precipitation of sulphides
following segregation of alloying elements into the remaining liquid. Microstructural
development of low carbon steel upon solidification has been observed in situ,
alloying element distributions were measured experimentally and sulphide
precipitates have been compared to the precipitates at the centreline of continuously
cast steel slabs. Microstructural development was similar in the two cases and some
aspects of alloying element segregation upon solidification of a slab can be simulated
experimentally by the use of the concentric solidification technique. There is a
remarkable similarity between the sequence of events decreased in the in-situ
observations and that occurring in industrially-cast slabs reported in the literature.
Sulphide precipitates at the centreline of concentrically solidified specimens are
similar in morphology and composition to precipitates in continuously cast steel slabs
and TEM analysis confirmed that FeTiS2 as well as MnS (containing iron) can form
on prior austenite grain boundaries in both cases.

The progression of the solid/liquid interface in plain Fe-C and Fe-Ni alloys was
simulated by using Diffusion Controlled TRAnsformation (DICTRA) software which
operates in conjunction with Thermo-Calc. Good correlation was found between
experimental results and computations. Solute build up in the liquid at the solid/liquid
interface was determined experimentally in Fe-Ni alloys and there was good
agreement between the calculated concentration gradient of nickel and experimental
measurements using an EPMA technique. Therefore, it is possible to determine
comparatively the centreline segregation with fairly elementary experimental
procedures and mathematical simulation at various steel compositions if DICTRA
and Thermo-Calc are provided with sufficiently accurate thermodynamic information.

Precipitates which formed in the solid state were assessed by carbon replication
techniques, transmission electron microscope studies and atom probe tomography.
Manganese and copper sulphides were the dominant sulphide precipitates. Copper
sulphides nucleated on manganese sulphides and formed a shell around rod-like and

IV
globular manganese sulphides. Iron did not dissolve in manganese sulphides and
therefore the manganese sulphides which formed in solid state have higher melting
points than sulphides formed on prior austenite grain boundaries at the centreline of
slab. Titanium nitrides were observed in various sizes and distributions. TiN acts as
nucleation sites for the precipitation of sulphides. An increase of the titanium content
from 0.008 wt% to 0.024 wt%, results in precipitation of a few micrometer TiN and a
decrease in the number of small cubic TiN precipitates.

Small particles (~ 10nm length and 3 nm thickness in size) that contain Ti, C, S and N
have been identified for the first time by the use of three-dimensional atom probe
tomography.

V
 Acknowledgements

I would like to express my deep gratitude to my supervisor professor Rian Dippenaar

for his encouragement, guidance and continuous support throughout all these years.
Many thanks to Dr. Dominic Phelan for his constructive comments on the modelling.
I owe sincere debt of gratitude to Mr. Mark Reid for training me to use the Laser-
Scanning Confocal Microscope, his assistance with experiments and his valuable
counsel in the course of this study.

I wish to acknowledge the following individuals from whom I have learned much: Dr.
David Wexler who gave me valuable insight into transmission electron microscopy,
Dr. Charlie Kong at the University of New South Wales for training me in Focused
Ion Beam, Dual Beam techniques and Mr. Alexander La Fontaine from the
University of Sydney for training me in three dimensional atom probe techniques.

I would like to acknowledge Mr. Keith Dilts from Nucor Steel and the courtesy of Dr
Kobus Geldenhuis for performing automated inclusion analysis on my samples.

I wish to thank the staff of the Faculty of Engineering, especially to Mr. Greg Tillman,
Mr. Nick Mackie and Dr. Zhixin Chen for their help and assistance. Many thanks to
the BlueScope Steel team especially Mr. Les Moore for conducting Electron Probe
Microanalyses.

I wish to express my heartfelt thanks to my family for their love and encouragement
that make me strong and free. Many thanks to all of my friends in this and other part
of the world for being always present and creating the special moments.

Finally I would like to thank BlueScope Steel and the University of Wollongong for
providing finantial support to the project.

VI
 Table of contents

CHAPTER 1: Introduction
1-1 Recent developments in linepipe steels 1
1-2 Classification of precipitates in continuously cast slab 3
1-3 Simulation of macrosegregation in continuously cast slab 4
1-4 Chapters contents 5

CHAPTER 2: Literature survey

2-1 Introduction 7
2-2 Titanium microalloyed steel 8
2-3 Development of low carbon microalloyed linepipe steels 9
2-4 The Fe-Ti-Al-O system 12
2-5 The Fe-Ti-C-N system 14
2-6 Sulphide inclusions in steels 18
2-6-1 Manganese sulphide classification in steels 20
2-6-2 Deformation of sulphide inclusions during hot rolling 25
2-6-3 Sulphide inclusions in titanium containing steels 28
2-7 Segregation in Continuous casting 33
2.7.1 Microsegregation 34
2.7.2 Macrosegregation 34
2.7.3 White band 36
2-8 In-situ observation of sulphide precipitation in steel 36
2-8-1 In-situ observation of macrosegregation in steel 38

CHAPTER 3: Experimental instruments and methodology

3-1 Scanning Electron Microscopy (SEM) 39
3-1-1 Sample preparation for optical and scanning electron microscopy 39
3-1-2 High Resolution Scanning Electron Microscopy (HR-SEM) 39

VII
3-2 Electron Probe Micro Analysing (EPMA) 40
3-3 Focused Ion Beam- Dual Beam (FIB) 40
3-3-1 Dual Beam 40
3-3-2 Three Dimensional Imaging and Reconstruction 41
3-4 High Resolution Transmission Electron Microscopy (HR-TEM) 42
3-4-1 Sample preparation for TEM analysis 42
3-4-1-1 Carbon replica 42
3-4-1-2 Selective Potentiostatic Etching by Electrolytic Dissolution 43
3-4-1-3 Focused Ion Beam 45
3-4-2 TEM analysis interpretation by Java Electron Microscopy
46
Software
3-5 High Temperature Laser Scanning Confocal Microscopy (HT-LSCM) 47
3-5-1 Concentric Solidification technique (CST) 49
3-5-2 Sample preparation for Laser Scanning Confocal Microscopy 50
3-6 Three dimensional local electrode Atom Probe 50
3-6-1 Sample preparation for Atom Probe investigations 51
3-6-2 Principles of three-Dimensional Atom Probe 52
3-6-3 Data analysis 53
3-7 Computational thermodynamics and kinetics 54
3-7-1 Thermo-Calc 54
3-7-2 DICTRA 55
3-7-2-1 DICTRA and diffusivities 56
3-7-2-1-1 Relations between diffusion coefficients and atomic
56
mobilities
3-7-2-1-2 Modelling of the atomic mobility 58

CHAPTER 4: Effect of titanium on the centerline sulphide precipitates of slabs

4-1 Introduction 60
4-2 Experimental technique 62
4-3 Inclusion analysis 63
4-4- Three dimensional imaging of precipitates 68
4-5 SEM evaluation of sulphide precipitates at the centerline of slabs 69
4-6 TEM evaluation of sulphides precipitates at the centerline of Slab A 72
4-7 TEM evaluation of sulphide precipitation at the centerline of Slab B 85
VIII
4-8 Comparison of the sulphides extracted from the centerline of Slabs A and B 90

CHAPTER 5: Characterisation of precipitates in low carbon, low manganese,

titanium added continuously cast steel
5-1 Introduction 98
5-2 Experimental method 99
5-3 TEM analyses of precipitates formed at the edge of Slab A 102
5-4 TEM analyses of precipitates formed at the edge of Slab B 106
5-5 TEM analysis of precipitates formed at the centerline of Slab A 108
5-6 TEM analyses of precipitates formed in slab centre of Slab B 112
5-7 Comparison of precipitation in different steels 114
5-8 Three dimensional Atom probe analysis 117
5-9- Summary 124

CHAPTER 6: Initial experiments on segregation study

6-1 Introduction 126
6-2 Experimental method 127
6-3 Results and discussion 129

CHAPTER 7: A novel technique to study segregation at the centerline of slabs

using Laser-Scanning Confocal Microscopy
7-1 Introduction 140
7-2 Experimental techniques 141
7-3 Study of segregation in Laser-Scanning Confocal Microscopy 141
7-4 TEM investigation of sulphides precipitated in segregated area of concentrically
157
solidified samples in LSCM
7-4-1 TEM analysis of sulphides precipitated in the segregated area of a
157
concentrically solidified specimen in LSCM prepared from steel A
7-4-2 TEM analysis of sulphide precipitates in the segregated area of
162
concentrically solidified specimen in the LSCM prepared from steel B
7-5 Comparison of sulphides in centerline of slabs with concentrically solidified
165
specimens

CHAPTER 8: Modeling of the solid/liquid interface progression in the concentric

IX
solidification technique
8-1. Introduction 167
8-2 Experimental data collection 168
8-3 Fe-0.1%C peritectic alloy Simulation 170
8-4 Heat transfer in concentrically solidified specimen 185
8-5 Fe-4.2%Ni peritectic alloy simulation 188
8-6 Conclusion 192

CHAPTER 9: Summary of findings, conclusions and recommendations

9-1 Summary of findings 194
9-2 Conclusion 198
9-3 Recommendations for future work 200

References 202
Appendices 213
Publications list 218

X
 List of Tables

Table (2-1): Chemical composition of invented steel 11

Table (2-2): Summary of observed precipitates in various titanium alloyed steel 31
Table (4-1): Bulk chemical composition of steel (percentage by mass) 62
Table (4-2): Minimum measured average diameter of inclusion at various positions of
slabs 67
Table (4-3): Comparison of angles calculated from indexed patterns and those
measured experimentally in the TEM 76
Table (4-4): Comparison between the angles measured experimentally in the TEM,
between the orientations shown in Figure (4-27) and calculated values 84
Table (4-5): Comparison of calculated angles between orientations in the indexed
patterns and the angles measured experimentally in the TEM 88
Table (4-6): Comparison of angles between orientations of indexed patterns in Figure
(4-33) and the experimentally measured values 90
Table (4-7): Composition of manganese sulphide and iron-titanium sulphide in Steels
A and B determined by EDS analysis in thin foils (weight percent) 91
Table (4-8): Atomic and ionic radii of elements which form iron-titanium sulphide 93
Table (5-1): Chemical compositions of the steels (weight percent) 99
Table (5-2): The composition, morphology and size of precipitates in Steels A and B 116
Table (6-1): Bulk chemical composition of steel (percentage by mass) 127
Table (7-1): d-spacing of the sulphide particle from three diffraction patterns
(nanometer) 160
Table (7-2): d-space of a particle from two diffraction patterns (Angstrom) 161
Table (8-1): Chemical composition of -ferrite in equilibrium with liquid in different
temperatures 171
Table (8-2): Summary of peritectic transformation temperatures for experimental and
simulated concentric solidification 181

XI
 List of Figures

Figure (2-1): Timeline development for high strength pipeline steels 10

Figure (2-2): Influence of manganese content on Charpy energy (at room temperature)
of low carbon steels (0.07-0.10 wt %) at varying sulphur levels 12
Figure (2-3): Oxygen saturation and domains of stability of oxides in the system Fe-
Al-Ti-O (weight percent) at 1600 C 14
Figure (2-4): Oxygen saturation and domains of stability of oxides in the system Fe-
Al-Ti-O (weight percent) at 1550 C 14
Figure (2-5): Calculated precipitation of nitrides, nitrogen rich carbonitrides and
carbides in 0.01 wt%Ti steel at various nitrogen contents 15
Figure (2-6): Solubility data for TiN 16
Figure (2-7): Calculated precipitation of MnS, Ti4C2S2 and TiN in low manganese
steel 17
Figure (2-8): Primary spherical MnS in Fe-2.5 wt%/.Mn-1.3 wt%/.S-0.3 wt%C, (a)
optical micrograph, (b) scanning electron micrograph 21
Figure (2-9): Dendritic MnS (a) Optical, (b) Scanning electron micrograph 22
Figure (2-10): Angular MnS (a) Optical micrograph, (b) Scanning electron micrograph 22
Figure (2-11): Monotectic MnS (a) Optical micrograph, (b) Scanning electron
micrograph 23
Figure (2-12): Rod like eutectic MnS (a) Optical micrograph, b) scanning electron
micrograph 23
Figure (2-13): Irregular eutectic MnS a) Optical micrograph b) Scanning electron
micrograph 24
Figure (2-14): Changes in phase equilibria in the Fe-MnS pseudo-binary system by the
addition of C and Si 25
Figure (2-15): The effect of titanium on the relative plasticity of the sulphides in low
carbon steels The effect of titanium on the relative plasticity of the sulphides in low
carbon steels 29
Figure (2-16): Microhardness values for the different (Mn, Me)S solid solutions for
different Me contents 30
Figure (2-17): Schematic phase diagram of the FeS-TiS pseudo-binary system 31
Figure (2-18): Typical examples of segregation in continuously cast slabs following

XII
Electro Magnetic Stirring (EMS) 33
Figure (2-19): microsegregation in low alloy steel: a) schematic drawing showing the
longitudinal and transverse cross-sections of dendrites; (b) solute distribution in the
transverse cross-section of the dendrite 34
Figure (2-20): Schematic diagram of concentric solidification 38
Figure (3-1): Column layout of the Dual Beam, FIB 41
Figure (3-2): Schematic of electrolytic cell Schematic of electrolytic cell 44
Figure (3-3): Differences of potential vs. current density curves between steels and
carbides in 10% AA type electrolyte 44
Figure (3-4): Differences of potential vs. current density curves between steels and
nitrides in 10% AA type electrolyte 44
Figure (3-5): Procedure of TEM sample preparation in FIB 46
Figure (3-6): Schematic representation of the confocal microscope 47
Figure (3-7): Confocal nature of optic 48
Figure (3-8): Schematic of laser-scanning confocal microscope chamber and sample
holder 48
Figure (3-9): Schematic diagram of concentric solidification 49
Figure (3-10): Schematic diagram of stage 1 electro-polishing 51
Figure (3-11): Micro-polishing in which the needle shaped specimen pierces a drop of
electrolyte suspended in a wire loop. The operation is monitored with an optical
microscope 52
Figure (3-12): Schematic diagram of Three-Dimensional Atom Probe 53
Figure (4-1): Examples of the appearance of centerline segregation 61
Figure (4-2): Schematic illustration of samples positions in slab 63
Figure (4-3): A light optical micrograph of sulphide precipitates at the centreline of an
industrially cast slab (unetched sample) 63
Figure (4-4): Chemical composition of inclusions on ternary phase diagrams, (a) Ti-
Al-Mn+S system of the edge of Slab B, (b) S-Al-Mn system of the edge of Slab B, (c)
Ti-Al-Mn+S system of the edge of Slab A, (b) S-Al-Mn system of the edge of Slab A 64
Figure (4-5): Chemical composition of inclusions on ternary phase diagrams, (a) S-Al-
Mn system of the centre of Slab B, (b) Ti-Al-Mn+S system of the centre of Slab B, (c)
S-Al-Mn system of the centre of Slab A, (b) Ti-Al-Mn+S system of the edge of Slab A 65
Figure (4-6): (a) Area fraction and (b) relative frequency of various inclusions at the
edge of Slabs A and B, (c) Area fraction and (d) relative frequency of various
XIII
inclusions at the centerline of Slabs A and B (sulphides at the edge refer to manganese
sulphides) 66
Figure (4-7): Position of detected inclusions at the centreline of Slabs A and B 67
Figure (4-8): (a) Schematic FIB-SEM 3D imaging method indicating the beam
directions, the sectioning and SEM imaging plane xy [103], (b) Pt layer deposited on
the surface of the selected particle 68
Figure (4-9): Reconstructed images of the selected sulphide precipitate 69
Figure (4-10): Concentration mapping (CM) of precipitates at the centreline of a Slab
A (EPMA) 70
Figure (4-11) SEM image and X-ray mapping of a precipitate in Steel B prepared by
HR-SEM 71
Figure (4-12): X-ray mapping of a precipitate in Steel A prepared by SEM 71
Figure (4-13): (a) Bright field image, (b) EDS trace of precipitate, (c-d) Selected area
diffraction patterns of the precipitate at the centreline of Slab A 72
Figure (4-14): (a) and (b) Bright field images of a precipitate from Steel A, (c)
Schematic illustration of the respective phases 73
Figure (4-15): (a) Bright field image, (b) EDS trace of elements, (c-e) Selected area
diffraction patterns of phase C1 in Figure (4-14) 74
Figure (4-16): (a) Bright field image, (b) EDS trace of elements of phase C2 in Figure
(4-14) 74
Figure (4-17): Selected area diffraction patterns of particle in three different simple
planes of a precipitate formed at the centreline of Steel A (Figure (4-14-a)) 75
Figure (4-18): (a) Three-dimensional view of FeTiS2 , (b) Schematic crystal structure 76
Figure (4-19): (a) Schematic diagram showing the Ewald sphere construction. O is the
origin of the reciprocal lattice, P a point on the Ewald sphere which is centred at X. (b)
Diagrams illustrating the relation between the Ewald sphere construction and the
geometry associated with the formation of TEM pattern where the effective camera
length, which is a function of the post-objective lens settings, is termed L 77
Figure (4-20): (a) and (b) Bright field image of a precipitate from Steel A, (c)
Schematic illustration of the constituent phases 79
Figure (4-21): (a) Bright field image, (b) EDS trace of elements, (c and d) Selected
area diffraction patterns of phase Q1 in Figure (4-20) 79
Figure (4-22): (a) Bright field image, (b) EDS trace of elements, (c-e) Selected area
diffraction patterns of phase Q2 in Figure (4-20) 80
XIV
Figure (4-23): (a) TEM sample prepared from a precipitate at the centreline of a slab
from Steel A by the FIB technique, (b) Bright field TEM image of the same particle 81
Figure (4-24): (a) Bright field image of a precipitate at the centreline of Steel A, (b)
Schematic illustration of constituent phases 81
Figure (4-25): (a) A bright field TEM image, (b) EDS trace and selected area
diffraction pattern of phase P1 in Figure (4-24) 82
Figure (4-26): (a) Bright field TEM image, (b) EDS trace, (c, d) Selected area
diffraction patterns of phase P2 in Figure (4-24) 83
Figure (4-27): (a) Bright field TEM image, (b) EDS trace, (c-e) Three selected area
diffraction patterns of phase P3 in Figure (4-24) 84
Figure (4-28): (a) Bright field image, (b) EDS trace of the precipitate, (c-d) Selected
area diffraction patterns of the precipitate extracted from the centreline of Steel B 86
Figure (4-29): (a) Bright field image, (b-d) Selected area diffraction patterns of a
particle extracted from centreline of Steel B 86
Figure (4-30): (a) Bright field image of a precipitate extracted from Steel A, (b)
Schematic illustration of the two phases 87
Figure (4-31): (a) EDS analysis pattern, (b-d) Selected area diffraction patterns
(SADP) of phase R1 in Figure 6 in three different tilts 88
Figure (4-32): X-ray map of the area containing phases R1 and R2 shown in Figure (4-
26) 89
Figure (4-33): (a) Bright field image, (b) Dark field image, (c-d) Selected Area
Diffraction Patterns (SADP) of phase R2 in Figure 6 in three low-index planes 90
Figure (4-34): Changes in the unit cell parameters a and c of solid solutions in the
FexTi(1-x)S system, plotted as a function of composition 94
Figure (4-35): Phase diagram of FeS-MnS 96
Figure (4-36): Modified area fraction and relative frequency of various inclusions at
the centreline of slabs A and B 97
Figure (5-1): Schematic illustration of samples positions in slab 100
Figure (5-2): Pseudo-binary Fe-C phase diagrams predicted by Thermo-Calc: (a) Fe-
C- 0.3% Mn- 0.01% S phase diagram, (b) Fe-C- 0.3% Mn- 0.01% S- 0.008% Ti phase
diagram, (c) Fe-C- 0.3% Mn- 0.01% S- 0.024% Ti phase diagram, (d) Fe-C- 0.3%
Mn- 0.006% S- 0.024% Ti phase diagram 101
Figure (5-3): Thermo-Calc prediction of the Fe- S- phase diagram when the iron
contains 0.1% C, 0.3% Mn and 0.024% Ti 102
XV
Figure (5-4): (a-d) Bright field images of precipitates extracted from the edge of Slab
A by carbon replica extraction, e) EDS analysis of rectangular precipitates 103
Figure (5-5): (a) A bright field TEM image of precipitates and (b) corresponding EDS
analysis 104
Figure (5-6): A bright field TEM image and corresponding Selected Area Diffraction
Pattern (SADP) of a precipitate formed at the edge of Slab A 105
Figure (5-7): A bright field TEM image of a thin foil prepared from the edge of Slab A 105
Figure (5-8): Bright field TEM images of precipitates formed at the edge of Slab A 106
Figure (5-9): Bright field TEM images of precipitates formed at the edge of Slab B 107
Figure (5-10): (a) Bright field TEM images of rod-like precipitates formed at the edge
of Slab B, (b) Bright field TEM images of precipitate in Figure (5-10-a) at higher
magnification, (c) EDS analysis 107
Figure (5-11): Bright field TEM images of sulphides extracted form the edge of Slab
B attached to TiN 108
Figure (5-12): HR-SEM images of precipitates formed within austenite grains at the
centreline of Slab A 109
Figure (5-13): Bright field TEM images of precipitates formed within austenite grains
at the centreline of Slab A 109
Figure (5-14): (a) Bright field TEM images of precipitates formed at the centreline of
Slab A, (b) EDS analysis of particle 1, (c) EDS analysis of particle 2, (d) EDS analysis
of particle 3 110
Figure (5-15): Bright field TEM images of precipitates formed at the centreline Slab A 111
Figure (5-16): Bright field TEM image of TiN formed at the centreline Slab A
together with corresponding Selected Area Diffraction Pattern (SADP) 111
Figure (5-17): Bright field TEM images of copper sulphide attached to TiN at the
centreline of Slab A at different magnifications 112
Figure (5-18): HR-SEM image of precipitates formed at the centreline of Slab B 112
Figure (5-19): (a) Bright field TEM image of a precipitate formed in centre of slab in
Steel B, (b) Selected area diffraction pattern of the precipitate, (c) EDS analysis of the
precipitate 113
Figure (5-20): Bright field TEM image of precipitates formed at the centre of Slab B 113
Figure (5-21): (a) Bright field TEM image of cubic precipitates formed at the centre of
Slab B together with (b) Selected area diffraction pattern of the marked precipitate 114
Figure (5-22): Temperature dependence of the solubility products of TiS and Ti4C2S2
XVI
reported in earlier research 115
Figure (5-23): Titanium and carbon atom map and corresponding 1.5 at% C iso-
concentration surface of a specimen prepared from the edge of Slab A 118
Figure (5-24): Concentration profile of elements across the precipitates in Figure (5-
23) 118
Figure (5-25): Titanium, sulphur, nitrogen and carbon atom map of a specimen which
was prepared from the centreline of Slab A 120
Figure (5-26): The 2 at% C iso-concentration surface of a specimen which was
prepared from the centreline of Slab A 121
Figure (5-27): The position of selected box perpendicular to precipitate 1 as well as
distribution of elements within the precipitate shown in Figure (5-26) 122
Figure (5-28): Concentration profile of elements across the precipitate 1 in Figure (5-
26) 122
Figure (5-29): Atomic map and concentration profile of elements across the precipitate
prepared by IVAS 123
Figure (5-30): Concentration profile of elements across the precipitate 2 in Figure (6-
23) 123
Figure (6-1): Schematic illustration of samples positions in slab prepared for
concentric solidification technique 128
Figure (6-2): Schematic illustration of solidification in continuously cast slab and
concentrically solidified specimen 128
Figure (6-3): Floated particles on the surface of liquid steel during heating in LSCM 129
Figure (6-4): Solidification progress and peritectic transformation observed in LSCM 130
Figure (6-5): -ferrite dendrites that formed in the molten pool, observed by LSCM 130
Figure (6-6): In-situ observation of sulphide precipitation on the surface of the LSCM
sample 131
Figure (6-7): Schematic illustration of solidification and precipitation by concentric
solidification technique 132
Figure (6-8): SEM photograph of a colony of precipitates 132
Figure (6-9): X-ray mapping of precipitates 133
Figure (6-10): Presence of liquid steel as well as two different solid phases (LSCM
sample) 134
Figure (6-11): Solubility product [Ti][S] for (TiS)s precipitation as a function of
temperature 135
XVII
Figure (6-12): Cross section of particles observed on the surface of concentrically
solidified specimen in the LSCM, (a) to (d) illustrate the cross section at different
magnifications 135
Figure (6-13): TEM sample prepared by FIB from the particles observed in the LSCM,
(a) Selected area, (b) Pt coating of interested area, (c) Prepared TEM sample, (d)
Thined prepared TEM sample in higher magnification 136
Figure (6-14): A bright field TEM image of layers in the sample shown in Figure (6-
13) 137
Figure (6-15): X-ray map prepared from TEM sample 138
Figure (6-16): Manganese sulphide precipitate surrounded by iron sulphide 139
Figure (7-1): Schematic view of a cross section (ABCD) of the concentrically
solidified specimen in LSCM 142
Figure (7-2): Cross section of a concentrically solidified sample 143
Figure (7-3): FeC phase diagram 144
Figure (7-4): (a) Typical microstructure of continuously cast slab in an Al-killed steel
with 0.15 wt% C, 1.4 wt% Mn, 0.46 wt% Si and 0.003 wt% S, (b) An optical
micrograph of the centerline segregation in 0.1 wt% C, 0.3 wt% Mn and 0.001 wt% S 145
Figure (7-5): Relative concentrations of Mn, Ti and S along a 7-mm length at the
centre of a concentrically solidified specimen (from steel A) at 20 C/min cooling rate
using line-scanning in electron probe microanalyses 146
Figure (7-6): Segregation profiles of C, P an Nb at the centreline of a continuously
cast slab 147
Figure (7-7): (a) Progression of -ferrite into the liquid pool (b) Progression of
austenite into the liquid pool following the peritectic reaction 148
Figure (7-8): Formation of dendrites ahead of the advancing solid/liquid interface in
the last remaining liquid 149
Figure (7-9): Relative concentrations of Mn along a 9.4-mm length at the centre of
concentrically solidified specimens (from Steel A) at different cooling rates using line-
scanning in EPMA analyses 150
Figure (7-10): Relative concentrations of Mn, Ti and S along a 9.4-mm length at the
centre of concentrically solidified specimens (from Steel A) at 5 and 80C/min
cooling rates using line-scanning in electron probe microanalyses 151
Figure (7-11): The segregated area of a concentrically solidified sample in LSCM,
prepared from steel A in optical microscope. Sulphide precipitates formed on prior
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austenite grain boundaries followed by primary ferrite formation on further cooling.
(a) As polished (b) Etched in 2% Nital 153
Figure (7-12): Sulphide precipitates and schematic clarification on prior austenite
grain boundaries observed at higher magnification a) Centreline of a slab (steel A), b)
Segregated area of a concentrically solidified specimen prepared from steel A 153
Figure (7-13): High resolution scanning electron microscopy images of precipitates in
segregated area 154
Figure (7-14): Concentration mapping (CM) of precipitates at the centreline of a slab
of steel A (EPMA) 155
Figure (7-15): Concentration mapping (CM) of precipitates in the segregated area of a
concentrically solidified specimen from Steel A: (a) EPMA results (b) x-ray mapping
by SEM 156
Figure (7-16): (a) Bright field image and EDS trace of precipitate formed in the
segregated area of a concentrically solidified specimen from steel A, (b) Selected area
diffraction patterns of the precipitate from two low-index planes 158
Figure (7-17): Bright field image and EDS spectrum of a particle formed on grain
boundary of a concentrically solidified specimen prepared from Steel A 158
Figure (7-18): Selected area diffraction patterns of the particle in three different low-
index planes of a precipitate formed in the segregated area of a concentrically
solidified specimen from steel A 159
Figure (7-19): Selected area diffraction pattern of the ferrite phase in contact with the
sulphide particle (Figure (7-17)) 159
Figure (7-20): Bright field image and EDS spectrum of the particle in segregated area
of the segregated area of a concentrically solidified specimen from Steel A 161
Figure (7-21): Selected area diffraction pattern of the particle in Figure (7-20) 161
Figure (7-22): (a, b) Bright field TEM images (c) EDS spectrum of the bright area (A)
(d) EDS trace of the dark area of the particle in the segregated area of concentrically
solidified specimen of steel B 162
Figure (7-23): (a) A bright field image of a particle in segregated area of a
concentrically solidified specimen in LSCM from steel B, (b) A schematic graph of
different phases in the particle 163
Figure (7-24): (a, b) Selected area diffraction patterns of iron sulphide in Figure (7-
23), (c) Selected area diffraction patterns of manganese sulphide in Figure (7-23) 163
Figure (7-25): (a) Bright field image, b) EDS trace of a precipitate prepared from the
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segregated area of a concentrically solidified specimen from Steel B; (b) A schematic
illustration of the particle 164
Figure (7-26): Selected area diffraction patterns of the precipitate in Figure (7-25)
which was prepared from the segregated area of a concentrically solidified specimen 165
from Steel B
Figure (8-1): ): Fe-C Phase diagram showing local equilibrium at the solid/liquid
interface in the liquid plus delta-ferrite two phase region of an Fe-0.18%C alloy at the
temperature shown 169
Figure (8-2): -ferrite growth and peritectic reaction in Fe-0.18 pct C alloy in a
concentrically solidified specimen prepared by LSCM at cooling rate of 10 C/min:
(a) Stable liquid pool at the initiation of solidification, (b) -ferrite growth into the
liquid, (c) Peritectic reaction, (d) Austenite growth into the liquid and transformation
of -ferrite to austenite 169
Figure (8-3): Interface position versus time for Case A at 5 C/min cooling rate 172
Figure (8-4): Schematic illustration of the concentric solidification technique with
essential temperatures shown (T3 > T2 >T1) 173
Figure (8-5): Interface position versus temperature, Case A with adjusted experimental
data at 5, 10 and 20C/min cooling rates 174
Figure (8-6): Weight percent of carbon versus distance at default diffusion coefficient
of carbon, 10, 100 and 1000 times faster carbon mobility in liquid, (a): 300 seconds
after the initiation of solidification at 5 C/min cooling rate, (b): 700 seconds after the
initiation of solidification at 5 C/min cooling 176
Figure (8-7): Confocal sample volume variation versus radius at constant thickness 176
Figure (8-8): Interface position versus temperature for Case A simulation system at 5,
10 and 20C/min cooling rate and higher carbon diffusivity in liquid 177
Figure (8-9): Comparison of experimental data with simulation results at various
carbon diffusivity in the liquid 178
Figure (8-10): Interface position versus temperature for Case B at 5, 10 and 20C/min
cooling rates 179
Figure (8-11): Interface position versus temperature for Case C simulations set at 5, 10
and 20C/min cooling rates 182
Figure (8-12): a) Carbon profile at 1 and 50 seconds after start of solidification at
20 C/min cooling rate for Case B set of simulations, b) Carbon profile at 30, 80 and
120 seconds at 20 C/min cooling rate for Case C set of simulations 184
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Figure (8-13): Schematic of the concentric solidification set-up, and corresponding
temperature distribution 187
Figure (8-14): Pseudo-binary phase diagram of Fe-Ni 188
Figure (8-15): Sequence of events happened during solidification of concentrically
solidified specimen at 5 C/min cooling rate with corresponded nickel profile which
measured experimentally and calculated by simulation 189
Figure (8-16): Comparison of nickel profile of a concentrically solidified specimen at
40 C/min cooling rate with nickel profile calculated by Case B set of simulations 190
Figure (8-17): One-dimensional diffusive model for banding in peritectic alloys
showing the mechanism and banding window 191

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